CN117624530A - Polyurethane resin and method for producing same - Google Patents

Polyurethane resin and method for producing same Download PDF

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Publication number
CN117624530A
CN117624530A CN202211152479.1A CN202211152479A CN117624530A CN 117624530 A CN117624530 A CN 117624530A CN 202211152479 A CN202211152479 A CN 202211152479A CN 117624530 A CN117624530 A CN 117624530A
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China
Prior art keywords
polyurethane resin
chain extender
weight percent
butanone
amount
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CN202211152479.1A
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Chinese (zh)
Inventor
廖德超
赵成礼
庄惠钧
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Nan Ya Plastics Corp
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Nan Ya Plastics Corp
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Priority claimed from TW111131089A external-priority patent/TW202409128A/en
Application filed by Nan Ya Plastics Corp filed Critical Nan Ya Plastics Corp
Publication of CN117624530A publication Critical patent/CN117624530A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2410/00—Soles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a polyurethane resin and a manufacturing method thereof, which comprises the following steps: mixing a polyester polyol, a polyether polyol, a first chain extender, diisocyanate and a mixed solvent, and carrying out polymerization reaction to obtain a prepolymer. A second chain extender is added to the prepolymer to perform a chain extension reaction to obtain the polyurethane resin. The mixed solvent comprises diethyl formamide and butanone, and the mass ratio of the diethyl formamide to the butanone in the mixed solvent is 0.45-1.80. The total addition amount of the first chain extender and the second chain extender is 0.9 to 2.5 weight percent based on 100 weight percent of the total weight of the polyurethane resin. The polyurethane resin has good processability, bending resistance and peeling strength.

Description

Polyurethane resin and method for producing same
Technical Field
The present invention relates to a polyurethane resin and a method for producing the same, and more particularly, to a polyurethane resin usable as a shoe material and a method for producing the same.
Background
Polyurethane is a polymer material with multiple functions and is generally used as a main raw material of artificial leather. Polyurethane resins with different hardness can be synthesized by adjusting the types and the compositions of the raw materials.
Conventional polyurethane resins are produced in a wet manufacturing process, and prior to curing, the polyurethane resin contains an organic solvent such as: dimethylformamide (DMF). Although the polyurethane resin containing dimethylformamide has good stability, the dimethylformamide has a high boiling point (153 ℃) and has the disadvantage of high energy consumption because the solvent needs to be vaporized at a high temperature during curing. In addition, dimethylformamide is a toxic substance in the tube array, and once absorbed by the human body, it is not easy to be discharged, so that it is easy to cause permanent damage to the human body.
Accordingly, the conventional polyurethane resin has a disadvantage of high curing temperature, and the polyurethane product has a problem of being not completely safe to be applied to all products due to safety concerns. Therefore, it has been an important problem to be solved by the industry to overcome the above-mentioned drawbacks by improving the production method and synthesizing a polyurethane resin without using dimethylformamide.
Disclosure of Invention
The invention aims to solve the technical problem of providing polyurethane resin and a manufacturing method thereof aiming at the defects of the prior art.
In order to solve the technical problems, one technical scheme adopted by the invention is to provide a manufacturing method of polyurethane resin. The method for producing the polyurethane resin comprises the following steps: mixing a polyester polyol, a polyether polyol, a first chain extender, diisocyanate and a mixed solvent, and carrying out polymerization reaction to obtain a prepolymer. A second chain extender is added to the prepolymer to perform a chain extension reaction to obtain the polyurethane resin. The mixed solvent comprises diethyl formamide and butanone, and the mass ratio of the diethyl formamide to the butanone in the mixed solvent is 0.45-1.80. The total addition amount of the first chain extender and the second chain extender is 0.9 to 2.5 weight percent based on 100 weight percent of the total weight of the polyurethane resin.
Further, the solvent in the polyurethane resin is removed at a processing temperature between 80 ℃ and 110 ℃.
Still further, the second chain extender is added in an amount of 3.5 to 4.8 times the amount of the first chain extender added.
Still further, the polyester polyol is contained in an amount of 18 to 28 weight percent, the polyether polyol is contained in an amount of 8 to 15 weight percent, and the diisocyanate is contained in an amount of 3 to 10 weight percent, based on 100 weight percent of the total weight of the polyurethane resin.
Further, the method for producing a polyurethane resin further comprises: after the chain extension reaction, butanone is added to the polyurethane resin so that the mass ratio of diethylformamide to butanone in the polyurethane resin is 0.09 to 0.35.
Further, the solid content of the polyurethane resin is 38% to 45%.
In order to solve the above technical problems, another technical solution adopted in the present invention is to provide a polyurethane resin, which is prepared by the above manufacturing method.
Further, the polyester polyol is polymerized by adipic acid and butanediol, and the polyether polyol is a linear polyether polyol with primary hydroxyl groups at two ends of a molecular chain.
Further, the polyurethane resin includes a soft segment in a proportion of 75 to 85 weight percent and a hard segment in a proportion of 15 to 25 weight percent.
Further, the viscosity of the polyurethane resin is 20000cps to 30000cps.
Further, the polyurethane resin has a weight average molecular weight of 90000 g/mol to 110000 g/mol.
Further, the peel strength of the polyurethane resin cured with respect to a polyurethane substrate is 12.0kg/3cm to 18.0kg/3cm.
The polyurethane resin and the manufacturing method thereof have the beneficial effects that the polyurethane resin can improve the processability, the bending resistance and the peeling strength of the polyurethane resin through the technical scheme that the mass ratio of the diethylformamide to the butanone in the mixed solvent is 0.45-1.80 and the total addition amount of the first chain extender and the second chain extender is 0.9-2.5 weight percent.
For a further understanding of the nature and the technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings, which are provided for purposes of reference only and are not intended to limit the invention.
Drawings
FIG. 1 is a flowchart showing the steps of the method for producing a polyurethane resin according to the present invention.
Detailed Description
The following is a description of embodiments of the present invention disclosed herein with respect to "polyurethane resin and method for manufacturing the same", and those skilled in the art will appreciate the advantages and effects of the present invention from the disclosure of the present invention. The invention is capable of other and different embodiments and its several details are capable of modification and variation in various respects, all from the point of view and application, all without departing from the spirit of the present invention. The drawings of the present invention are merely schematic illustrations, and are not intended to be drawn to actual dimensions. The following embodiments will further illustrate the related art content of the present invention in detail, but the disclosure is not intended to limit the scope of the present invention. In addition, the term "or" as used herein shall include any one or combination of more of the associated listed items as the case may be.
In order to solve the problems, the invention provides a method for manufacturing polyurethane resin, which does not need to use dimethylformamide in the manufacturing process, and can reduce the toxicity threat of the product to human body. And the prepared polyurethane resin has the advantages of good processability, good bending resistance and high peeling strength, and can meet the characteristic requirement of applying the polyurethane resin to shoe materials in the market at present.
Referring to fig. 1, the method for producing polyurethane resin of the present invention comprises the steps of: mixing polyester polyol, polyether polyol, first chain extender, diisocyanate and mixed solvent, and performing polymerization reaction to obtain prepolymer (step S1); adding a second chain extender to the prepolymer, and performing a chain extension reaction to obtain a polyurethane resin (step S2); butanone is added to the polyurethane resin so that the solid content of the polyurethane resin is 38% to 45% (step S3).
The solid components forming the polyurethane resin include: polyester polyol, polyether polyol, chain extender (first chain extender and second chain extender) and diisocyanate. The polyester polyol is contained in an amount of 48 to 63 weight percent, the polyether polyol is contained in an amount of 20 to 30 weight percent, the chain extender is contained in an amount of 1.5 to 8 weight percent, and the diisocyanate is contained in an amount of 10 to 20 weight percent, based on 100 weight percent of the total weight of the solid components in the polyurethane resin.
The polyurethane resin comprises a soft segment and a hard segment, wherein the soft segment is composed of polyester polyol and polyether polyol, the hard segment is composed of diisocyanate and a chain extender, and the blending of the soft segment and the hard segment can lead the polyurethane resin to have better bending resistance.
In a preferred embodiment, the weight proportion of the soft segments is higher than the weight proportion of the hard segments. Specifically, the polyurethane resin includes 75 to 85 weight percent soft segments and 15 to 25 weight percent hard segments, based on 100 weight percent of the total weight of solid components in the polyurethane resin. In this way, the polyurethane resin can have good physical properties after polymerization, and can be applied to shoe materials.
In a preferred embodiment, the polyester polyol is an adipic acid-based polyester polyol. For example, monomers for synthesizing the polyester polyol may include adipic acid and butanediol, the polyester polyol having a number average molecular weight of 1000 g/mol to 3000 g/mol, a hydroxyl number of 35 to 39, and an acid number of 0.4 to 0.6. However, the invention is not limited thereto.
In a preferred embodiment, the polyether polyol is a linear polyether polyol and has primary hydroxyl groups at the molecular terminals. For example, the polyether polyol may be tetrahydrofuran-average polyether (number average molecular weight of 1000 g/mol to 3000 g/mol) or polypropylene glycol (number average molecular weight of 1000 g/mol to 4000 g/mol), and the polyether polyol has a number average molecular weight of 1000 g/mol to 4000 g/mol. However, the invention is not limited thereto.
In a preferred embodiment, the first chain extender and the second chain extender are each independently selected from the group consisting of: ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol. The first chain extender and the second chain extender may be the same or different, and in a preferred embodiment, the first chain extender is the same as the second chain extender.
In a preferred embodiment, the diisocyanate may be selected from the group consisting of: diphenylmethane diisocyanate (methylenediphenyl diisocyanate, MDI), toluene diisocyanate (toluene diisocyanate, TDI) and isophorone diisocyanate (isophorone diisocyanate, IPDI). However, the invention is not limited thereto.
In the present invention, the chain extender is added in the step S1 and the step S2, respectively, and the addition amount of the second chain extender is controlled to be larger than the addition amount of the first chain extender, so that the flex resistance of the polyurethane resin can be improved. In a preferred embodiment, the amount of the second chain extender added is 3.5 to 4.8 times the amount of the first chain extender added, and in particular, the amount of the second chain extender added may be 3.6, 3.8, 4.0, 4.2, 4.4 or 4.6 times the amount of the first chain extender added.
In the invention, the chain extender is added stepwise, so that the polyurethane resin has better processability, peel strength and bending resistance. The addition of the first chain extender may first suitably lengthen the molecular chain length of the polyurethane resin. The addition of the second chain extender further enables the polyurethane resin to have ideal molecular chain length, and improves the processability, peel strength and flexing resistance of the polyurethane resin.
It is noted that, when the addition amount of the second chain extender is too low, the structural strength of the polyurethane resin is insufficient, which negatively affects the processability, peel strength and flex resistance of the polyurethane resin. Specifically, the first chain extender may be added in an amount of 0.2 to 0.6 weight percent and the second chain extender may be added in an amount of 0.9 to 2.5 weight percent, based on 100 weight percent of the total weight of the polyurethane resin, including the solid and liquid components.
The timing of adding the second chain extender also affects the properties of the polyurethane resin in order to polymerize the desired polyurethane resin. In a preferred embodiment, when the isocyanate (-NCO) content of the prepolymer is 1.0 to 2.0 weight percent, a second chain extender is added to the prepolymer to perform step S2.
On the other hand, in order to provide good compatibility and reactivity of solid components (polyester polyol, polyether polyol, chain extender and diisocyanate), the invention selects diethyl formamide and butanone as solvents (liquid components) to replace toxic dimethyl formamide.
During the polymerization (steps S1 and S2), the addition of diethylformamide can promote the compatibility and reactivity of the polyurethane resin, but too much or too little diethylformamide can negatively affect the compatibility and physical properties of the polyurethane resin. Therefore, the invention controls the addition amount of the diethyl formamide, and mixes a proper amount of butanone to adjust the solid content of the polyurethane resin so as to be beneficial to the progress of the polymerization reaction.
In a preferred embodiment, the mass ratio of diethylformamide to butanone in the mixed solvent is 0.45 to 1.80, and specifically, the mass ratio of diethylformamide to butanone in the mixed solvent may be a value in an arithmetic series having a tolerance of 0.05 between 0.45 and 1.80 (e.g., 0.45, 0.50, 0.55..1.70, 1.75, 1.80).
Specifically, the amount of diethylformamide added is 5 to 16 weight percent based on 100 weight percent of the total weight of the polyurethane resin (including solid and liquid components). For example, the diethylformamide may be added in an amount of 6 weight percent, 8 weight percent, 10 weight percent, 12 weight percent, or 14 weight percent.
The butanone added in step S1 can maintain the solid content of the polyurethane resin at a concentration favorable for the reaction. The solid content of the polyurethane resin may be adjusted to 38% to 45% by adding butanone in step S3. And, the addition of butanone can reduce the evaporating temperature of the solvent in the polyurethane resin to reduce the energy consumption required for curing the polyurethane resin. Specifically, the solvent (butanone and diethylformamide) in the polyurethane resin may be removed at a processing temperature of 80 ℃ to 110 ℃.
Specifically, the total weight (including solid and liquid components) of the polyurethane resin is 100 wt%, the amount of butanone added in step S1 is 6 wt% to 12 wt%, and the amount of butanone added in step S3 is 32 wt% to 45 wt%. The total amount of butanone added to the polyurethane resin is 40 to 60 weight percent.
In order to confirm the advantages of the polyurethane resin of the present invention, such as good processability, good flex resistance and high peel strength, polyurethane resins of examples 1 to 4 (E1 to E4) and comparative examples 1 to 3 (C1 to C3) were formulated according to the following procedure, and the specific addition amounts of the respective components are shown in table 1.
In step S1, adipic acid polyester polyol (polyester polyol), tetrahydrofuran homo-polyether (polyether polyol), 1, 6-hexanediol (first chain extender), diethylformamide (DEF) and butanone (MEK) (mixed solvent) are added into a reaction tank, and the temperature is raised to 70 ℃ with continuous stirring. Then, diphenylmethane diisocyanate (diisocyanate) and a small amount of catalyst were added to the reaction tank, and the temperature was further raised to 78 ℃ and reacted for two hours to prepare a prepolymer.
In step S2, 1, 6-hexanediol (second chain extender) is added to the prepolymer and reacted at a temperature of 78℃for one hour to obtain a polyurethane resin.
In step S3, after the polyurethane resin is cooled to 45 ℃ or lower, butanone is added to dilute the polyurethane resin to a solids content of 38% to 45% (preferably 39% to 41%).
After the completion of the formulation, the polyurethane resins of examples 1 to 4 (E1 to E4) and comparative examples 1 to 3 (C1 to C3) were subjected to tests for viscosity, weight average molecular weight, processability, peel strength and flex resistance, respectively.
The viscosity is measured by a viscometer (brand: BROOKFIELD, model: DV-E). The weight average molecular weight was measured using a gel permeation analyzer (brand: SHIMADZU, model: LC-40 XR). Processability is evaluated for whether the coatability is abnormal at a processing temperature of 80 ℃ to 110 ℃, and if there is no abnormality, it is denoted by "OK", and if there is an abnormal defect, it is denoted by "NG". The peel strength was measured by a universal tensile tester (brand: SHIMADZU, model: AG-X). The evaluation of the room temperature flex resistance was carried out by using a flex tester (brand: GOTECH, model: GT-7006-V50) at an angle of 22.5℃and a frequency of 100 times/min and 25 ℃ X10 ten thousand times, and the flex test was carried out with the appearance of no abnormal defect and no breakage indicated by "OK" and with the appearance of abnormal defect and breakage indicated by "NG". The low temperature flex resistance was evaluated by using a flex tester (brand: GOTECH, model: GT-7006-V50) and performing a flex test at an angle of 22.5 degrees, a frequency of 100 times/minute and a frequency of-10 ℃ X1 ten thousand times, wherein the appearance of no abnormal defect and no breakage was represented by "OK" and the appearance of abnormal defect and breakage was represented by "NG".
TABLE 1
From the results of Table 1, it can be seen that the polyurethane resin of the present invention has good processability, can remove the solvent at a processing temperature of 80℃to 110℃and has good coating smoothness. The polyurethane resin has bending resistance under the environment of normal temperature and low temperature, can resist bending test for one hundred thousand times under normal temperature (25 ℃) and can resist bending test for one ten thousand times under low temperature (-10 ℃).
The peel strength of the polyurethane resin of the present invention is more than 12kg/3cm. Specifically, the peel strength of the polyurethane resin with respect to a polyurethane substrate may be 12.0kg/3cm to 18.0kg/3cm. That is, the polyurethane resin has good bonding strength with respect to the polyurethane material.
In addition, the viscosity of the polyurethane resin of the present invention may be 20000cps to 30000cps, and preferably, the viscosity of the polyurethane resin is 25000cps to 30000cps. The weight average molecular weight of the polyurethane resin of the present invention may be 90000 g/mol to 110000 g/mol, and preferably the weight average molecular weight of the polyurethane resin is 92000 g/mol to 109000 g/mol. However, the invention is not limited thereto.
From the content of comparative example 1, it is found that the polyurethane resin of the present invention cannot be obtained when the addition concentration of the chain extender (first chain extender and second chain extender) is insufficient (less than 0.9 weight percent). The second chain extender is preferably added at a concentration of 0.9 to 2.5 weight percent.
As is clear from the contents of comparative examples 2 and 3, the mass ratio of diethylformamide to butanone in the mixed solvent affects the characteristics of the polyurethane resin, and when the mass ratio of diethylformamide to butanone is less than 0.9 weight percent (comparative example 2) or greater than 2.5 weight percent (comparative example 3), the polyurethane resin of the present invention cannot be obtained.
Advantageous effects of the embodiment
The polyurethane resin and the manufacturing method thereof have the beneficial effects that the polyurethane resin can improve the processability, the bending resistance and the peeling strength of the polyurethane resin through the technical scheme that the mass ratio of the diethylformamide to the butanone in the mixed solvent is 0.45-1.80 and the total addition amount of the first chain extender and the second chain extender is 0.9-2.5 weight percent.
Furthermore, the invention can achieve the effect of improving the compatibility and the reactivity between the solid components in the polyurethane resin and can lead the polyurethane resin to have good processability through the technical scheme that the mixed solvent comprises the diethyl formamide and the butanone.
Furthermore, the invention improves the processability, the bending resistance and the peeling strength of the polyurethane resin by adopting the technical scheme that the addition amount of the second chain extender is 3.5 to 4.8 times that of the first chain extender.
Furthermore, the invention improves the processability of polyurethane resin by adding butanone into polyurethane resin after chain extension reaction to make the mass ratio of diethylformamide to butanone in polyurethane resin be 0.09-0.35.
The foregoing disclosure is only a preferred embodiment of the present invention and is not intended to limit the scope of the claims, so that all equivalent technical changes made by the application of the present invention and the accompanying drawings are included in the scope of the claims.

Claims (12)

1. A method for producing a polyurethane resin, comprising:
mixing a polyester polyol, a polyether polyol, a first chain extender, diisocyanate and a mixed solvent, and performing polymerization reaction to obtain a prepolymer; wherein the mixed solvent comprises diethyl formamide and butanone, and the mass ratio of the diethyl formamide to the butanone in the mixed solvent is 0.45-1.80; and
adding a second chain extender into the prepolymer to perform chain extension reaction so as to obtain polyurethane resin;
wherein the total addition amount of the first chain extender and the second chain extender is 0.9 to 2.5 weight percent based on 100 weight percent of the total weight of the polyurethane resin.
2. The method of claim 1, wherein the solvent in the polyurethane resin is removed at a processing temperature between 80 ℃ and 110 ℃.
3. The method according to claim 1, wherein the second chain extender is added in an amount 3.5 to 4.8 times the amount of the first chain extender.
4. The production method according to claim 1, wherein the polyester polyol is contained in an amount of 18 to 28 weight percent, the polyether polyol is contained in an amount of 8 to 15 weight percent, and the diisocyanate is contained in an amount of 3 to 10 weight percent, based on 100 weight percent of the total weight of the polyurethane resin.
5. The manufacturing method according to claim 1, characterized by further comprising: after the chain extension reaction, butanone is added to the polyurethane resin so that the mass ratio of diethylformamide to butanone in the polyurethane resin is 0.09 to 0.35.
6. The method according to claim 5, wherein the polyurethane resin has a solid content of 38% to 45%.
7. A polyurethane resin, characterized in that the polyurethane resin is produced by the production method according to any one of claims 1 to 6.
8. The polyurethane resin according to claim 7, wherein the polyester polyol is obtained by polymerizing adipic acid with butanediol, and the polyether polyol is a linear polyether polyol having primary hydroxyl groups at both ends of a molecular chain.
9. The polyurethane resin of claim 7, wherein the polyurethane resin comprises a soft segment in a proportion of 75 to 85 weight percent and a hard segment in a proportion of 15 to 25 weight percent.
10. The polyurethane resin according to claim 7, wherein the polyurethane resin has a viscosity of 20000cps to 30000cps.
11. The polyurethane resin according to claim 7, wherein the polyurethane resin has a weight average molecular weight of 90000 g/mol to 110000 g/mol.
12. The polyurethane resin according to claim 7, wherein the peel strength of the polyurethane resin cured with respect to a polyurethane substrate is 12.0kg/3cm to 18.0kg/3cm.
CN202211152479.1A 2022-08-18 2022-09-21 Polyurethane resin and method for producing same Pending CN117624530A (en)

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